Photographic development



Ufl t dqsws P efl PHOTOGRAPHICDEYELOPMENT Jan Ja ken, H v an Andre :Emile Van .Dormael,

lieverleeLouvain, Belgium, Ph t -.Pmducten N- V1! Mort el, B a Bel ian nr y N Drawing, Application January 21, 1952, Serial No. 267,496,

Claims priority, applicatipn Great Britain J,anuary 26, 1951 Claims. (Cl."9588) This invention relates .to a photographic developing process and to photographic developers, especially for use in color photography.

The p-phenylene diamines which are used as color developing agents "have a number of drawbacks. 'They are highly allergic to :the skin. Developing solutions which contain p-p'henylene diamines darken which is due to oxidation "by air, and at thesame'time the potency-of the solution is diminished.

assignors to Gevaert .i

Patented Nov. 23, 1954 images, or of color images. In the latter case, the presence of a color coupler either in the photographic ma terial or in the developing solution is required.

The developing agents according teaur invention produce on color development the same dyestuif as the developingagents of the formula Y-Ar-NHz since the group CZZSOsM is split oil. This fact facilitates considerably the replacement of compounds of the formula Y-Ar-NHz by corresponding compounds of Formula II.

The lattercompounds, except for those derived from acroleine, are but'little or not at all allergic to the skin,

Also, develeping solutions on ini g the d veloping ag nts cf our invention d nut rk n un er the influenc er air.

.Developin ol' ions cont ini g our v lopin ag nts hould lsoicent in he usu l In order to avoid these disadvantages, it has been pro 7 posed to introduce into the molecule of the developing agent, either into thenucleus or into the substituents of the amino group, acidic groups'which render the developing agents more water-soluble. However, in most of these cases, the developing power is substantially reduced by .such vintroduction.

A further proposal is to introduce substituent-S con.- tai i g acidic groups into .the free NI-Iz groups of the developing agents. ';Such develop ng agents correspond to the following formula:

wherein A is a divalent hydrocarbon nucleus; X'Tis COOM or fiSOsM (wherein M is hydrogen or a water-soluble salt-forming cation, preferably an alkali metal such as sodium or potassium); 'and Y is -OH, NH2, NHR or --NR2 in ortho- .,or para-position to the nitrogen atom (wherein R is a hydrocarbon radical). i

It is an object of our present invention to provide a new process for developing a reducible silver salt image in a photographic silvr halide emulsion layer.

It is another object of our invention to provide a new process for forming a colored image by developing a reducible silver salt image in a photographic silver "halide emulsion layer.

It is .a further :object .of the inventionlto providenew photographic developing solutions.

Further objects "will become apparent from the followii ng edien s ch s an al aline substan e, and a re tra u such as po a ium bromide. The addition :of a :sulphite is generally not required, although it may be used in some cases, but further substances may be added, such as :a further ,der

, veloping agent, a buffering agent as, for instance, di-

sodium hydrogen phosphate, and an emulsion hardener as, for instance, formaldehydew'The solution may be composed before use from two or more solutions, concentrated solutions, or powders. 1

The developing agents may be added to the photographic materialas well. Inthis' case'pthe material may 'beydeveloped, after-exposure, in an alkaline solution;

'Ourdeveloping agents may be used, as is known, for

PIDducing anegativeor a reversed image from an exposed color photographic material by color development. The

silver imagesimu'ltaneousl-y formed with the dye image :as well as the negative silver image in a reversal process may be eliminated. 1

The following examples serve to illustrate this invention, without limiting, however, the scope thereof.

Example 1 To a solution :of 4.4 .g. acetaldehyde in 40 gram. water are added, while cooling in ice, 20 g. sodium bisulphite. After also adding 16.4 g. NzN-diethyl-p-phenylene diamine, the mixture is heated on the water bath for 13 minutes, while shaking. After cooling, the crystals formed are sucked off and purified bycrystallization from water. -Melting :po'int: 143-145 .C. The product .obtained corresponds :to the following probable formula:

Alternately, 150 ccm. water are saturated with S02 .at room temperature and 16.4 g. NzN-diethyl-p-phenylene diamine are dissolved therein. By adding 4.4 g. :acetaldehyde, the mixture becomes hot. After cooling, the precipitate formed is sucked *ofi and washed with ethanol. Melting point: 14 0143 C. After recrystallization from water, the melting :point is 143-145 C. The product obtained likewise corresponds to the probable Formula III.

Example) To a solution of 25g. sodium bisulphite and 11.6 g.

' race onein .60 an. wa er are added :37 .5 g. NrN-diethyl- 'v-p nylen l i mine- This mixture is shaken at 2. C. lmtil a crystalli e p cipitate is formed and th fN:N- .diethyl p-phenylene diam'ine is almost dlSSQ'lVfid, whereafter the crystals formed are sucked off- The. Pr pihydroearbon radical, optionally substituted pr linked to I the carbon atom in ortho-position to Y, and R and 'R;

tggethermay-eomplete a heterocyclig: 'nu'cleusyoptjonal'l y substituted, e. g.,-by-a hydroxyl-or a 'su'lpho group); and Z-and Z are hydrogen or alkyl' or substituted alkyl.

The developing agents according to formula (If) ma b pr pa d. cniu ta by a t on f a c mpound of I mu Ii H w th n a dehyde e a et ne Z 0 anda bisjulpl iteor sulphur dioxide.

' evei n n e s sn vi e u ed .fo n 'cdr e- ":tion 0f "black and-wh'ite images, especially fiire grain ar as t t is thcreughly washed with acet e.- Melting p int: above 3 30 .C. The product obtainedcorcl'sponds to the following 'pmbable formula:

C2115 CH3 Nash-some CH2 Example 3 g. bisulphitein-200ccm. water, 'th reflux cundens'er, "are'added shaking. While thesh-akiug s n cL. g. diethyl -p-p nyl diamine deed and the mixture is heated for 10 minutes on the water bath. After cooling, the crystals formed are sucked ofl and purified by crystallization from an ethanol-water mixture l/ 1. Melting point: l66-168 C. The product obtained corresponds to the following probable formula:

N-- I: H--C H-S 03H C2115 CHz-CHr-S OaNB Example 4 Example 5 11.5 g. dry sodium bisulphite and 3.5 g. croton aldehyde are dissolved in 40 com. water by heating. After cooling, the solution is shaken with 9.9 g. N:N-diethylp-phenylene diamine for 4 hours and next concentrated in vacuo. The precipitate formed is sucked off and washed with acetone. Melting point: above 330 C. The product obtained corresponds to the following probable formula:

(VII) CzHt (12H; Hr-CHSO:NB

Example 6 15.9 g. dry sodium bisulphite and 11 g. iso-butyric aldehyde are dissolved in 40 com. water by heating on the water bath. To this solution is added a solution of 32 g. NzN-diethyl-p-phenylene diamine sulphate in 100 com. water, and the whole is heated for 2 hours on the water bath. Crystals form which after cooling are sucked off and recrystallized from water. Melting point: 136-139" C. The product obtained corresponds to the following probable formula:

vni) 02H /N NH-CH-SOaH 02H CH4 5 r Example 7 To a solution of 10.4 g. dry sodium bisulphite and 4.4 g. acetaldehyde in 100 com. water are added 13 g. p-phenylene diamine. Upon shaking, the p-phenylene diamine first dissolves. After about. 15 minutes, a precipitate is formed which is sucked off and recrystallized from an aqueous solution of ethanol 50%. Melting point: 142143 C. The product obtained corresponds to the following probable formula:

Example 8 2.2 g. paraldehyde are dissolved in a solution of 5.2 g. dry sodium bisulphite in 30 com. water. After heating for 2 hours on the water bath with 11.5 g. N-ethyl- N-beta-hydroxy ethyl-p-phenylene diamine sulphate, and after cooling, the precipitate formed is sucked oif, washed with acetone and recrystallized from water.

4 Melting point: 128-130 C. The product obtained corresponds to the following probable formula:

Example 9 5.2 g. dry sodium bisulphite and 2.2 g. paraldehyde are dissolved in 30 com. water and heated for 2 hours on the water bath with 10.7 g. 2-amino5-diethylaminotoluene hydrochloride. After cooling, the precipitate formed is sucked off and washed with acetone. Melting point: 135-l38 C. The product obtained corresponds to the following probable formula:

X1 0211. on;

NQNH( JHSOsH Cm Example 10 5.2 g. dry sodium bisulphite and 2.2 g. paraldehyde are dissolved in 30 com. water and heated for 2 hours on the water bath with 9.2 g. mono-ethyl-p-phenylene diamine sulphate. After cooling, the precipitate formed is sucked off and washed with acetone. Melting point: 151-l53 C. The product obtained corresponds to the following probable formula:

(XII) OH;

Example 11 2.8 g. dry sodium bisulphite dissolved in 10 ccm. water and 2.5 ccm. of an aqueous solution of formaldehyde 36% are heated for 15 minutes at 40-50 C. with 3.5 g. sodium bicarbonate and 5.4 g. N-methyl-6'aminotetra-hydroquincline-oxalate in com. water. The precipitate formed is sucked off and recrystallized from diluted alcohol. Melting point: 149l50 C. The product obtained corresponds to the following probable orrnu a:

(XIII) CH:

NH-CHPSOaH u.

Example I 2 0.5 g. paraldehyde and 1.25 g. dry sodium bisulphite are dissolved in 10 com. water and heated for 2 hours on the water bath with 2.1 g. N-(p-aminophenyl)- piperidine. After cooling, the precipitate formed is sucked off and recrystallized from water. Melting point: 139 C. The product obtained corresponds to the following probable formula:

(XIV) CHz-GH:

c 1 \rNn-onsoan GHQ-CZ (3113 Example 13 A silver bromo-iodide gelatine emulsion layer is developed in a bath of the following composition:

A developing substance according to Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 Metol (methyl-para-aminophenol-sulphate) 2 Sodium sulphite (cryst.) Trisodium phosphate 3.5 Potassium bromide 1.

Water to 1000 ccm.

is washed, fixed, washed again and dried. A fine-grain black-and-white image is obtained. Besides gelatine, also collodion, a water-permeable cellulose ester, or another water-permeable synthetic resin may be used as a binding agent for the silver halide.

"Example 14 A silver halide gelatine emulsion layer, after exposure, is developed in a bath of the following composition:

Sodium sulphite (cryst. g 110 Sodium carbonate ('cryst.) .g .100 Water to 1000 ccm.

(B') l -phenyl 3-(m-nitrophenyl)-5-pyrazolone g 1 Alcohol ccm (Before usa B is added to 'A.)

is washed, freed from silver with .a potassium .Lferricyanide solution, Washed again, ffixed, washed .for a third time .and dried. .A pure -magenta image obtained.

Example I5 A multi-layer material comprising;

is exposed, developed in a metolhydroquinone developer, washed, exposed to white light, developed in a bath composed as follows:

A color developing substance according to Examples 1, 2, 3, 4,5,6, 8, 9, 10, 11 or 12 Sodium sulphite (cryst.) 5 Potassium carbonate 75 Potassium bromide 2.5

Water to 1000 ccm.

washed again, freed from silver with a potassium ferricyanide solution, washed once more, fixed, finally washed and dried. A positive color image is obtained.

Example 16 A photographic multi-layer material as described in Example 15, containing sensitizers and color couplers fast to difiusion, may after exposure be directly developed in the above mentioned color developing bath and further treated as in Example 15. The negative color image obtained may be copied upon similar multi-layer material, and by treatment in a like manner as to obtain the negative, a positive copy image is obtained.

We claim:

1. Process for developing a reducible silver salt image in a photographic silver halide emulsion layer, WhlCh comprises treating such layer with a developer containing a compound according to the formula:

wherein M is a member selected from the group consisting of hydrogen and a water-soluble salt-forming cation; Ar is p-phenylene; Y is a substituent of Ar 1n para-position to the nitrogen atom, selected from the group consisting of an amino group substituted by a hydrocarbon radical, an amino group subst tuted by two hydrocarbon radicals, an amino group substituted by two substituents completing together a heterocyclic radical, and an amino group substituted by a substituent linked to the carbon atom in ortho-position to Y; and Z and Z' are members selected from the group consisting of hydrogen and alkyl.

J6 'QJTroeess'for forming a colored image by developing a reducible silver salt image in a photographic silver halide emulsion layer, which comprises treating such layer with a developer containing arcompound according wherein .M :Jis auznentlber :selected from the :group :consisting of hydrogen and a water-soluble salt forming cation; Ar is p-phenylene; Y is a substituent of Ar in para-position to the nitrogen atom, selected from the group consisting ofan' amino groupsfibstituted by a hydrocarbon radical, an amino group substituted by two hydrocarbon radicals, an amino group substituted by two substituents completing together a heterocyclic radical, and an amino group substituted by a substituent linked to the carbon atom in ortho-position to Y; and Z and Z are members selected from the-group consisting of hydrogen and alkyl.

3. Process for forming-a colored image by developing a reducible silver salt' image *in *a photographic silver halide emulsion layer, which comprises treating such layer with a developer containing a ..compound according to the formula:

layer with a developer containing a compound according to the formula:

(II) Z Y-Ar-NH-C-SOzM wherein M is a member selected from the group consist mg of hydrogen and a water-soluble salt-forming cation; Ar is p-phenylene; Y is a substituent of Ar in para-position to the nitrogen atom, selected from the group consisting of an amino group substituted by a hydrocarbon radical, an amino group substituted by two hydrocarbon radicals, and an amino group substituted by two substituents completing together a heterocyclic radical; and Z and Z are members selected from the group consisting of hydrogen and alkyl.

5. Process for forming a colored image by developing a reducible silver salt image in a photographic silver halide emulsion layer, which comprises treating such layer with a developer containing a compound according to the formula:

(III) C2115 CH \N Gm n; son

(VI) CzHs \N ONE on son 7. Process for forming a colored image by developing a reducible silver salt image in a photographic silver hallde emulslon layer, which comprises treating such layer with a developer containing a compound according to the formula:

8. Process for forming a colored image by developing a reducible silver salt image in a photographic silver halide emulsion layer, which comprises treating such layer with a developer containing a compound according to the formula:

9. Process for forming a colored image by developing a reducible silver salt image in a photographic silver halide emulsion layer, which comprises treating such layer with a developer containing a compound according to the formula:

(XIII) CH2 10. A photographic developing solution containing an alkaline substance, a restrainer, a preserving agent, and

8 as a silver halide agent a compound according to the formula:

Y-Ar--NHC-SO:M

wherein M is a member selected from the group consisting of hydrogen and a water-soluble salt-forming cation; Ar is p-phenylene; Y is a substituent of Ar in para-position to the nitrogen atom, selected from the group consisting of an amino group substituted by a hydrocarbon radical, an amino group substituted by two hydrocarbon radicals, an amino group substituted by two substituents completing together a heterocyclic radical, and an amino group substituted by a substituent linked to the carbon atom in ortho-position to Y; and Z and Z are members selected from the group consisting of hydrogen and alkyl.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,163,166 Wilmanns June 30, 1939 2,570,116 Gunther Oct. 2, 1951 2,575,027 Schmidt Nov. 13, 1951 2,578,292 Donovan Dec. 11, 1951 OTHER REFERENCES Beilstein, 4th ed., vol. 13, p. 83. Chem. Abst., vol. 12, pp. 366-367. 

1. PROCESS FOR DEVELOPING A REDUCIBLE SILVER SALT IMAGE IN A PHOTOGRAPHIC SILVR HALIDE EMULSION LAYER, WHICH COMPRISES TREATING SUCH LAYER WITH A DEVELOPER CONTAINING A COMPOUND ACCORDING TO THE FORMULA: (II) 